Hippuristanol → HCID 49864735、化合物

HRID 1677836ノート

反応式

HRID 1677836 の反応式
[CH3:1][C@@H:2]1[C:31]([CH3:33])([CH3:32])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C@H:22]([OH:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C@@H:13]([OH:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1>N1C=CC=CC=1.O=[Cr](=O)(O[Cr](=O)([O-])=O)[O-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.CCOCC>[CH3:1][C@@H:2]1[C:31]([CH3:32])([CH3:33])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C@H:22]([OH:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C:13](=[O:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1.[CH3:1][C@@H:2]1[C:31]([CH3:32])([CH3:33])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C:22](=[O:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C:13](=[O:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1

参加物

6

反応物 1

HCID 9981822Hippuristanol

生成物 2

HCID 49864734HCID 49864734、化合物収率 28%HCID 49864735HCID 49864735、化合物収率 56%

試薬・触媒・溶媒 3

HCID 1049Pyridine溶媒HCID 3283Diethyl Ether溶媒HCID 2724130Cornforth reagent溶媒

実験手順

Oxidation of hippuristanol (1) to yield hippuristanol 11-one (4) and hippuristanol 3, 11-dione (5). To an ice-cooled solution of hippuristanol (1, 31.7 mg) in pyridine (0.5 mL), Cornforth reagent (0.7 mL) was added dropwise. The mixture was kept stirring for 30 min. in an ice bath, then 3 hr at RT. The mixture was taken up in ether and the suspension was filtered. The filtrate was washed with dilute hydrochloric acid, dried over Na2SO4, and concentrated. The resulting product was separated on silica TLC (CHCl3/EtOAc, 3:1, v/v) to give 8.8 mg of hippuristanol 11-one (4, 28%) and 17.7 mg of hippuristanol 3,11-dione (5, 56%). Hippuristanol 3,11-dione (5). white crystals. mp 181-183.5° C.; 1H NMR (CDCl3) δ 4.42 (m, 2H), 3.02 (s, 1H), 2.82 (ddd, J=13.0, 6.5, 2.0 Hz, 1H), 2.63 (d, J=12.0 Hz, 1H), 2.45 (dt, J=6.5, 14.5 Hz, 1H), 2.37 (dd, J=13.0, 8.0 Hz, 1H), 1.31 (s, 3H), 1.22 (s, 6H), 1.20 (s, 3H), 1.11 (s, 3H), 0.99 (d, J=7.0 Hz, 3H); 13C NMR (CDCl3) δ 211.6, 210.0, 115.0, 84.9, 80.4, 79.1, 63.9, 63.4, 58.8, 54.5, 46.9, 46.3, 44.3, 41.8, 40.5, 38.0, 37.0, 35.5, 35.2, 33.7, 32.4, 28.7, 28.5, 28.2, 23.0, 17.3, 14.8, 11.0; IR (KBr) 3510, 1695 cm−1; EIMS m/z 458 (M+, 5), 316 (92), 84 (100%).

後処理

  1. additionwas added dropwise
  2. custom3 hr
  3. customat RT
  4. filtrationthe suspension was filtered
  5. washThe filtrate was washed with dilute hydrochloric acid
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe resulting product was separated on silica TLC (CHCl3/EtOAc, 3:1

出典と根拠

ORDレコード
ord-c35980a653c54caf8eb75a8521aa20ad
出典データセット
uspto-grants-2011_08
特許番号
US08008346B2

反応ノート

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